Thermoadhesive composition and articles coated therewith



Patented Oct. 3, 1939 UNITED, STATES THERMOADHESIVE COMPOSITION AND ARTICLES COATED THEREWITH Ernest L. Kallander, Framingham, Mass, as-

slgnor to Dennison Manufacturing Company,

Framingham, Mass., chusetts No Drawing.

Claims.

This invention relates to thermo-adhesive compositions and articles coated therewith. While not restricted thereto, it deals more especially p with paper tapes or similar thin, flexible articles 5 coated with such compositions and designed to be stuck or bonded to their own and other surfaces under the momentary application of moderate heat thereto. One exacting sphere of use for thermo-adhesive tape is the application of such tape as abinderabout the skirt portion of a hood of "Cellophane or equivalent sheet material sometimes used'to protect the mouth of a milk bottle. For such purpose, the thermo-adhesive coating on'the tape should properly he possessed of various combined qualiti s, including quick acquisition of adhesive or bonding quality under the application .of'moderate heat, strong adhesiveness or bond even to very smooth surfaces, such as Cellophane, both while it is in plastic or'thermo-activated state and after it has set, little tendency to slip or flow away from its base or the surface against which it is applied in its thermo-activated state, and sufiicient hardness or freedom from plasticity under room or prevailing temperature conditions to resist blocking or sticking to itself when in plied or q roll form. It is further desirable that the thermo-adhesive coating be waterproof, non-toxic,

free from malodor, and of attractive appearance.

30 It is known that polyvinyl resins-answer admirably many of the foregoing requirements for a thermo-adhesive. However, those polyvinyl resins, such as polyvinyl acetate and/or polyvinyl chloride, that have the desired quick thermo-adhesive response, are generally too prone to be possessedwof sensible plasticity or flow at room temperatures, especially those likely to prevail in the summertime or neara steam radiator, in consequence of which superposed plies of material coated therewith, such as a roll of tape coated therewith, may in effect become a solid block whose plies are so-bonded or fused together as to be practically useless. I have found that there are various substances compatible with polyvinyl resins and capable of hardening them sufficiently to do away with their undesirable plasticity or flow characteristics at room or prevailing temperatures and that shellac is espe-. cially useful for this purpose in that it does not materially detract from the strong thermo-adhesive bond to be had from the polyvinyl resin itself. On the other hand, the blending of shellac or equivalent hardening agent with polyvinyl resin in amount sufficient to yield a thermo adhesive composition of the desired hardness or non-plastic character at room temperature is attended by an undesirable increase in the softening point of the composition; that is, its thermoadhesive response is adversely'affected unduly by the shellac or equivalent hardening compoa corporation of- Massa- Application January 26, 1937, Serial No. 122,409

nent. I have further found,.however, that there are other'resins compatible with both the polyvinyl resin and the shellac and capable of serving as fluxing agents for both these latter ingredients without detracting significantly from the strong bond to be had from the polyvinyl resin alone or from the blend of such resin with the shellac. Thus, I have found that the artificial resins marketed by Hercules PowderCompany under the trade-mark Petrex, e. g. Petrex No. 13, are especially valuable as fluxes for shellac-polyvinyl resin compositions in the sense that they can be blended therewith in amount to impart to the resulting blends quick thermoadhesive response while enabling the attainment in the resulting blends of the various other desiderata hereinbefore mentioned, including adequate hardness at room temperature, strong or tenaciousbond to various surfaces, etc. These various Petrex resins are .prepared by condensing derivatives of the terpcne series with suitable polycarboxylic organic acids, such as succinic and maleic acids, and esterifying' with suitable polyhydric alcohols, such as the aliphatic polyhydric alcohols. They are available as resins of various softening or melting points, but for the purposes hereof, it is preferable that the Petrex resin employed be of a softening or melting point range of about 90 to 130 F., as determined by a somewhat modified penetrometer method of measuring softening points hereinafter described. The Petrex resins are characterized by their hardness or resistance to flow at room temperature and their comparatively sharp softening or melting points as well as their excellent compatibility with both polyvinyl resins and shellac. In using the term compatibility herein as applied to the Petrex resin and the shellac, I mean the ability of these substances to form a substantially homogeneous or non-separating mixture orblend with the polyvinyl resin and with each other either upon being fused under heat or upon being treated with various organic liquids or organic liquid mixtures constituting solvents common to all these three substances. 1

It might be noted that a Petrex resin alone is wholly unsatisfactory as a thermo-adhesive coating by reason of the fact that it tends to run or melt away from the mark to be bonded and does not give an adequately tenacious bond, particularly in moist or thermo-activated state. The unsuitability of the Petrex resins in this regard is readily appreciated from their relatively low and sharp melting points. I have found that for some purposes, however, a thermo-adhesive composition consisting essentially of a, blend of the' polyvinyl resin and Petrex resins, such as hereinbefore described, may be satisfactory, particularly when the vinyl resin content represents the present" invention comprehends thermoadhesive compositions consisting essentially of polyvinyl resins and the "Petrex resins, yet the preferred compositions hereof contain also shellac or equivalent hardening agent, as already described.

There are gums or resins that might be used in lieu of or together with the shellac as hardening agents in the thermo-adhesive compositions hereof, including colophony or ordinary rosin.

However, because ordinary rosin detracts materially from the bonding tenacity of the composition hereof when used in amount to harden the composition adequately, probably imparting in some measure to the polyvinyl resin its own brittleness or friability, it is not to be recommended as a shellac substitute in thecomposition hereof, excepting when the composition is to serve purposes requiring only a comparatively low degree of bonding tenacity. Again, it is possible to replacethe "Petrex" resins in the thermo-adhesive compositions hereof by other suitable fluxing resins or gums, such as alcohol-soluble ester gum and a para'coumarone indene type of resin. However, such other fluxing resins as I have investigated for the purpose 'of the compositions hereof are inferior to the Petrex resins especially as regards their compatibility with the polyvinyl resins and shellac; and I hence distinctly prefer to use the Petrex resins as fluxes in the com- V positions hereof.

:walls of 'a .milk bottle;

The present invention will now be described more specifically in terms ofthe manufacture of thermo-adhesive paper tape'to be used in bindmg in place the skirt portions of a CellophaneT,

paper, or equivalent hood about the external neck In this .connection, it might be remarked that the hoods must be pulled down over the tops of the filled bottles and bound' in place very quickly and, accordingly, that the thermo-adhesive tape used for such purpose must develop .thermo-adhesiveness almost instantly. Indeed, the hooding machines are usually designed to run the bottles at a rate upwards of per minute; and, it is thus seen that the hot irons or clamps of the machine employed for actlvating the tape and causing. it to bond to the Cellophane" or other hood material and its end portions into lapping relationship have very little time inwhlch to accomplish these desiredzresults. Although the tape-activating irons re preferably maintained very hot (upwards, of.

F.)-, the time of pressure contact between the irons and the tape is so short that the tempera.-

ture imparted to the tape is much lower (probably downwardsof 300 F.) and, in anyevent, moderate enough not to scorch or otherwise inlure the tape. The paper base for such tape is preferably surface-sized and surface-filled, 'as with a casein coating composition containing clay or other filler and, if desired, pigment or dye. Because of the smooth surface d low penetrability of such paper base, a mi um amount of the composition hereof is necessary-for develop- 1 13 has a softe 1 ment.

ing a thermo-adhesive coating of requisite thickness and, upon being thermally activated, the coating does not tend to sink or become dissipated into the body of the paper.

The thermo-a'dhesive compositions for coating such a paper base may be prepared by dissolvin approximately six parts by weight of vinylite A7, two parts of shellac, and two parts of "Petrex No. 13" in an amount of volatile organic solvent to form a solution of, say, about 40% solute content, at which solute content the solution may be readily and smoothly spread on the paper surface. The 'Vinylite A7 has a softeng point of about 101 F., as measured ,byt e penetrometer method hereinafter given; and the shellac, which is preferably one of good commercial grade, cleanliness, solubility, andnormal wax content, has a softening point of about 157 F. Shellac that is of undue age or that has been degenerated by heat is unsuitable for the thermo-adhesive compositions hereof. A good medium for blending or dissolving the foregoing three components constitutin ing point of about; 148 F. and the Petrex No.

a preferred thermo-adhesive composition hereof is made up-by weight of 25 parts of denatured alcohol, 15 parts of benzol, and 10 parts of ethyl acetate. The resulting physically homogeneous solution, which is a comparatively thick or viscous liquid, may be spread onto the surface of the paper by any suitable machine, for instance, by the conventional spreading machine wherein a knife or doctor blade serves to regulate the thickness of coating deposited on the paper. The solution may be applied to a web of the paper as itis being progressively run through the machine to deposit a smooth coating in an amount or thickness of, say, about 7 pounds of solids or thermo-adhesive composition over a paper area of 250,000 square inches, whereupon the solutioncoated paper may be passed progressively over hot drying rolls or through-a hot-air drying chamber to evaporate the solvent and. the dried paper cooled to about room temperature preparatory to being wound into a roll. The coated paper may then be progressively unwound from the roll and cut into the desired narrow ribbons or tape, which maybe wound into rolls for storage and ship- It is generally preferable that the back or inactive face of the thermo-adhesive tapes hereof be coated with a cellulose derivative, such as nitrocellulose or cellulose acetate, as sucha coated surface bonds better to the activated thermoadhesive coating than a plan paper surface'and it also tends to inhibit blocking of the rolled or convoluted tape. Accordingly, the back or inactive face of the paper to be cut into the tape hereof is preferably coated with nitrocellulose or equivalent cellulose derivative solution. Only a very thin coating of the nitrocellulose need be carried by the back face of the tape, for instance, a coating amounting to aslittle as about 1.5

pounds of nitrocellulose per 250,000 square inches .ofpa'per surface. The nitrocellulose coating may be deposited and dried on the paper in very much the same way as the thermo-adhesive composition from a nitrocellulose solution of, say, about 8% guncotton content (-second viscosity guncotton) in acetone. Of course, nitrocellulose solutions of various other concentrations prepared from other kinds of guncotton and other nitrocellulose solvents might be employed. In

some instances, the nitrocellulose solution ap--' plied to the paper may advantageously contain specific and preferred components having para nitrocellulose-plasticizer, as a plasticizer tends to keep the sheet flat, that is, to destroy such curling tendencies as might otherwise exist therein. However, the plasticizers employed for this purpose should not be such usual nitrocelluloseplasticizers as tricresyl phosphate and dibutyl pthallate, as these also have a decided plasticizing or solvent action on the thermo-adhesive such compositions.

compositions hereof and hence tend to cause blocking of the rolled thermo-adhesive tapes hereof when used in the nitrocellulose or back face coating of such tapes. ,There are particular nitrocellulose-plasticizers that have very little plasticizing effect on the thermo-adhesive compositons hereof; and it is only 'such plasticizers, if at all, that I employ in the nitrocellulose or back face coating of the thermo-adhesive tapes hereof. Among such plasticizing agents may be mentioned the alkyl acetyl 'ricinoleates, particularly butyl acetyl ricinoleate, which, although very effective in its plasticizing action on nitrocellulose; have insignificant plasticizing or solvent action on the thermo-adhesive compositions hereof. Thus, I have used various artificial resins, such as alkyd, phenolic and vinyl resins, in the nitrocellulose or back face coating of the thermo-adhesive tape hereof in the amount of 30% and higher, based on the weight of the nitrocellulose, without encountering blocking troubles in the rolled tape.

It is possible 'to vary the proportions of each of the components of the thermo-adhesive coating compositions hereof while realizing to a'satisfactory degree the various desiderata already noted for the thermo-adhesive tape coated with It is preferable, however, that the thermo adhesive composition or coating of such tape have a softening point ranging from about to 145 F. as measured by. the method hereinafter given, and be sufiiciently strongly adhesive or bonded at such temperatures to enable the lapping of end portions of the'tape into a'ring about a bottle neck Without break-away or parting of the lapping portions immediately upon removal of the momentary lapping pressure of the hot clamping irons under the parting stress existing at such portions. I have found that a thermo-adhesive compositon containing the three specific components of the example hereinbefore given answers the foregoing and other requirements with its content of shellac ranging from about 15% to 50% its Vinylite A7 content ranging from 25% to 75%, and its Petrex No. 13 content ranging from about 15% to 50%. All factors considered, including suitably low softening point and tenacity. of bond in: both thermo-activated and set states, I have found that a thermo-adhesive composition containing the proportions by weight of these three components (20 Petrex resin, 20 shellac, and 60 vinyl resin), as prescribed in the example hereinbefore given, represents an optimum composition for the purposes hereof, for its softening point, about 'C., is very quickly attained with very little danger of injuring the paper base on which it occurs as a coating and with little tendency for the coating to'become slippery or so fluent as to'run off the paper base; and it bonds strongly at such temperature, insomu'ch that an attempt to break the bond results in tions or ranges of the three components of the compositions hereof, although cited for three able to apply the thermo-adhesive compositions,

hereof to paper as solutions in suitable volatile organic solvents or solvent mixtures, yet it is possible to fuse or melt the three solid components of such compositions and thereby blend them to form a pyhsically homogeneous, liquid or fused mixture and to heat the mixture to about 250 to 300 F., at which temperatures the fused mixture is sufficiently fluent to enable smooth and easy. spreading on a paper surface, whereupon the spread coating'of thermo-adhesive composition carried by the paper may be allowed to set or congeal to its normally glossy and nontacky state. A

The thermo-adhesive-v compositions hereof may be applied to articles other than tape that are designed to be bonded by thermal activation to their own and to other surfaces. Thus, such compositions may be applied as coatings to labels, stickers, fabric, or other articles intended .tobe bonded by thermal activation to various surfaces, particularly very smooth or glossy surfaces resistant to sticking by common adhesives. The thermo-adhesive compositions hereof may also be applied to such smooth or glossy sheet materials' as metal foilsand Cellophane whose It might be noted that VinyIite A7 is the acetic ester of polyvinyl alcohol and that the chloride esters as well as theacetic esters are also useful for the purposes hereof. Indeed, the vinyl resins for the purpose hereof may be mixtures or compounds of the chloride and acetic esters or other vinyl resins having the desired properties and put out under such a variety of trade names as "Gelva, Alvar", Formavar,

Vinnapas, Mowillith", Vinyloid, and Vinylite. It might be further remarked that there are other artificial resins that have physical and chemical characteristics more or less similar to those of the vinyl resins and that may be used for the purposes hereof in lieu of the vinyl resins. Thus, the more soluble of the polystyrol resins, which are sold under the trade names fVictron and Resoglaz may be used in lieu of the vinyl resins. Other artificial resins serviceable for the purposes hereof in lieu of the vinyl resins are the so-called acrylate resins, for instance,those sold under the trade names Pontolite and Acryloid. These acrylate resins are usually alkyl esters of acrylic acid and methylacrylic acid that polymerize under suitable conditions to yield resins of a hardness, solubility, and a rubbery or stringy adhesiveness or tackiness under the action of heat or relatively small amount of solvent simliar to that displayed by the vinyl and styrol resins. In

using the expression vinyl resins" in the fore-- i a the softening point of the resin is an arbitrary Sons, Ltd., London, and sold by the Industrial Book Company, Inc.,' 280 Broadway, New York, N. Y., for the chemistry of these reactions).

The melting points hereinbefore noted were determined in the following manner. A 10-gram sample of resin is put in a round tin dish having a diameter of 2" and a height of The resin is melted over a Bunsen burner; and, if there are several components, they are stirred together thoroughly until well mixed. The resin is then placed in an oven at 100 centigrade for about one-half hour, taken out and put in a dish of water at about the same temperature. It is then placed on the platform of a Dow penetrometer, which is described in Eimer .and Amends catalogue of 1927 (catalogue No. 16,386). This penetrometer is used for asphalt testing and is designed on the same principle as the New York Testing Lab type, but is not equipped- /8" brass rod slightly rounded at the end, is-

brought in contact with the resinfithe reading noted, and the holding lever released. After 15 seconds, the reading is noted and the penetration recorded, as well as the temperature at that time, by means of a thermometer in the water,

jacket. Successive readings are taken-as many as possible-as the material cools down, preferably at 10 Fahrenheit intervals. These successive needle-penetration readings are taken, of course, under separate applications of the weighted needle-at the different observed temperatures of'the resin being tested and are plotted as the ordinates" on coordinate graph paper with the observed temperatures of the resin on the coordinate scale." A smooth curve is drawn through the points representing the conjunctive* penetration and temperature conditions of the resin and the temperature point at which thecurve intersects the ordinate scale at a pe'netration value of 10 is taken as the softening or.

melting point of the resin. It will be appreciated that this point of intersection chosen herein as one'and that any other point of intersection within a resonabie range. might be chosen. However, the' softening point values hereingiven are in terms of the particular or precise testing method described herein, a

I claim: 1 I I 1. A therm'o-adhesive composition comprising a polyvinyl resin having a softening point of about 148 F., shellac having a softening point of about 157 F., and a fluxing resin having a softening point falling within-a range of about 90 to 130 F., said polyvinyl resin,'.shellac, and fluxing resin all being compatible, said polyvinyl resin being present in said composition in the amount of about to 75%, said sheiba amount or about 15% to 50%,and said fluxing resin in the amount of about 15% to 5 0%, based on the weight of the composition, and said fluxing resin being prepared by condensing derivatives of-the terpene series with polycarboxylic acid and esterifying with polyhydric alcohol. r

2. A thermo-adhesive composition comprising a polyvinyl resin having a softening point of about 148 F., shellac having a softening point impart to said composition a softening point of about 134 F., and said fluxing resin being prepared by condensing derivatives of the terpene series with pclycarboxylic acid and esterifying with polyhydric alcohol.

cinthe' 3. A thermo-adhesive composition comprising a polyvinyl resin having a softening point of about 148 F. and a fluxing resin compatible therewith and having a softening point falling within a range of about 90 to 130 F., said polyvinyl resin being present in said composition in the amount of about 25% to 75%, based on the weight of the composition, andsaid fluxing resin being prepared by condensing derivatives of the terpene series with polycarboxylic acid and esterifying with polyhydric alcohol.

4. A thermo-adhesive composition having a softening point within a range of about 115 to 135 F. and comprising. polyvinyl resin. shellac, and a fluxing resin having a softening point within a'range of about 90 to 130 F., said polyvinyl resin, shellac, and fluxing resin all being compatible, said polyvinyl resin being present in said composition in the amount of about 25% to 75%, said shellac in the amount of about 15% to 50%, and said fluxing resin in the amount of about 15% to 50%, based on the weight of the composition, and said fluxing resin 'being prepared by condensing derivatives of the terpene series with polycarboxylic acid and esterifying with polyhydric alcohol. v

'5. A thermo-adhesive composition having a softening point within a range of about 115 'to having a softening point of about 157 F., and a fluxing resin having a softening point within a f range of about to F., said polyvinyl acetate, shellac, and fluxingaresin all being compatible, said polyvinyl acetate being present in said composition in the amount ofabout 25% to 75%, said'shellac intheamount of abmut 15% to 50%; and said fluxing resin in the amount of about 15% to 50%, based on the" weight 'of the ERNEST L. KALLANDER.

.F. and comprising polyvinyl acetate, shellac 

